The Problems of Sulphur: Reviews in Coal Science

technology.

Related titles

Coke

Monograph on Victorian Brown Coals

Introduction to Carbon Science

Part 1

Chemical desulphurisation of coal

Outline

Introduction to Chemical desulphurisation of coal

Chapter 1: Introduction

Chapter 2: Sulphur in coal

Chapter 3: Requirements for chemically cleaned coal

Chapter 4: Chemistry of coal cleaning

Chapter 5: Processes for the chemical cleaning of coal

Chapter 6: Evaluation of processes

Chapter 7: Current research on chemistry of desulphurisation reactions

Chapter 8: Conclusions

Introduction to Chemical desulphurisation of coal

1 Summary

The recent literature relating to the chemical desulphurisation of coal is reviewed. Following an assessment of the forms of organic and pyritic sulphur in coal and the potential chemical reactions these may undergo, fifteen processes for the chemical cleaning of coal which are currently under development are described and evaluated. These include the PETC process; the Ames wet oxidation process; the Ledgemont process; the ARCO promoted oxidative process; the TRW Meyers desulphurisation process; the TRW Gravichem process; the JPL chlorinolysis process; the KVB process; the Battelle hydrothermal process; the TRW Gravimelt process; the General Electric microwave treatment process; the Aqua-refined coal process; the Magnex process; the IGT flash desulphurisation process; and a chemical comminution process. It is concluded that with the present state of knowledge the additional sulphur removed by chemical cleaning processes compared with that removed by physical cleaning processes is insufficient to justify the additional complexity and hence cost of preparation. Much more fundamental research is required to elucidate the modes of occurrence and chemistry of sulphur in coal, particularly of organic sulphur, before the efficiency of the chemical cleaning of coal can be improved.

Chapter 1

Introduction

Publisher Summary

This chapter presents the requirements for a chemically cleaned coal and also the descriptions of chemical coal cleaning processes under development. The chapter also presents an evaluation of these processes. The combustion of coal for the generation of electric power and process heat necessitates the control of pollutants that are potentially harmful to man or the environment. It is found that although the control of emissions of particulates, nitrogen oxides, and trace elements is receiving attention, most effort has been directed toward the control of emissions of sulfur in the form of sulfur dioxide. Emissions of sulfur dioxide from coal combustion may be controlled by factors such as the use of low sulfur content coal, the pretreatment of coal to remove sulfur, and the retention of sulfur during combustion. Reserves of that contain sufficiently low concentrations of sulfur to enable sulfur dioxide emission standards to be met when the coals are burned are limited and restricted to specific geographical locations. The costs of coal conversion processes preclude, at present, the use of coal-derived liquids or gases for combustion. Processes that retain sulfur during combustion are currently being developed.

The combustion of coal for the generation of electric power and process heat necessitates the control of pollutants which are potentially harmful to man or the environment. Although the control of emissions of particulates, nitrogen oxides and trace elements is receiving attention, most effort has been directed towards the control of emissions of sulphur in the form of sulphur dioxide.

Emissions of sulphur dioxide from coal combustion may be controlled by one or more of the following:

1. The use of low sulphur content coal.

2. The pretreatment of coal to remove sulphur.

3. The retention of sulphur during combustion.

4. The post-combustion treatment of flue gases.

5. The conversion of coal into a liquid or gaseous form.

Reserves of coals which contain sufficiently low concentrations of sulphur to enable sulphur dioxide emission standards to be met when the coals are burned are limited and restricted to specific geographical locations. The costs of coal conversion processes preclude, at present, the use of coal derived liquids or gases for combustion. Processes which retain sulphur during combustion are currently being developed. The sulphur retention property of limestone is being employed in fluidised bed combustion and in the production of limestone/coal pellets for use in stoker fired boilers (Gaimmar et al., 1980). The most widely adopted method of controlling emissions of sulphur dioxide is by the use of flue gas desulphurisation (FGD). However, the reliability of flue gas scrubbers is often such that two or three systems in series are required to ensure sufficient control of sulphur dioxide. The cost of FGD represents a significant proportion of the equipment cost of a coal fired power station. This proportion increases as the size of the plant decreases making FGD prohibitively expensive for the small industrial coal fired boiler (Prior, 1977).

The remaining option for controlling sulphur emissions is that of pretreating coal to remove sulphur prior to combustion. The physical cleaning of coal to remove mineral matter by washing and gravity separation techniques is already widely practised in the coal industry. These processes also remove between 30 and 90% of the pyritic sulphur associated with the mineral matter in coal (McCandless and Cantos, 1979). However, because coal is inevitably rejected with the higher density material of high sulphur content the yield of coal may be reduced by as much as 40%. In addition, as much as 50% of the sulphur in coal may be associated with the organic portion of coal and is therefore not removed. In order to decrease the sulphur content of such coals to acceptable levels it is necessary to treat the coal chemically to remove both organic and pyritic sulphur. This is chemical coal cleaning (Ruether, 1979). No such process is, as yet, available commercially although several are under active development.

The majority of chemical coal cleaning processes are designed to produce coals with sufficiently low sulphur contents to permit their combustion for power generation without the use of FGD. However, several of the processes also remove mineral matter, trace elements and other compounds as well as modifying the basic combustion properties of the coal. Chemically cleaned coal may therefore find other applications such as in the production of coal/oil mixtures, coal/water mixtures or for use in magnetohydrodynamic (MHD) power generation (Meyers, 1980).

This part presents the requirements for a chemically cleaned coal, descriptions of processes under development and an evaluation of these processes. Chapter 7 discusses subsequent research into the chemistry of desulphurisation reactions and its implications for coal cleaning. Firstly however, it is necessary to understand the nature of sulphur in coal.

Chapter 2

Sulphur in coal

Publisher Summary

This chapter reviews the presence of sulfur as one of the impurities in coal. Sulfur is recognized as one of the major impurities in coal. Its concentration in world coal resources varies between 0.19% and 10% although the range for the world’s economically recoverable coal reserves is narrower, at 0.38–5.32%. Sulfur occurs in coal as pyritic sulfur, organic sulfur, sulfate salts, and elemental sulfur. Pyritic and organic sulfur together account for the large majority of sulfur in coal. Sulfate sulfur occurs chiefly as gypsum and iron sulfate, the latter normally resulting from oxidation of iron pyrite during the storage of coal. The concentration of sulfate sulfur in coal is generally less than 0.1%. This, together with its solubility in water, means that this form of sulfur is of little concern during coal cleaning. The concentration of elemental sulfur in coal is also small, generally less than 0.2%. There is evidence to suggest that the content of thiols is substantially larger in lignites and high volatile bituminous coals than in low volatile coals. The proportion of thiophenic sulfur is also greater in higher ranked coals than in lower ones.

Sulphur is recognised as one of the major impurities in coal. Its concentration in world coal resources varies between 0.19% and 10% (Yurovskii, 1960) although the range for the world’s economically recoverable coal reserves is narrower, at 0.38 to 5.32% (Meyers, 1977).

Sulphur occurs in coal as:

1. pyritic sulphur;

2. organic sulphur;

3. sulphate salts;

4. elemental sulphur.

Pyritic and organic sulphur together account for the large majority of sulphur in coal. Sulphate sulphur occurs chiefly as gypsum and iron sulphate, the latter normally resulting from the oxidation of iron pyrite during the storage of coal. The concentration of sulphate sulphur in coal is generally less than 0.1%. This, together with its solubility in water, means that this form of sulphur is of little concern during coal cleaning. The concentration of elemental sulphur in coal is also small, generally less than 0.2% (Greer, 1979).

Pyritic sulphur

Iron sulphide, FeS2, the primary inorganic source of sulphur in coal, occurs in two crystalline habits: pyrite (cubic) and marcasite (orthorhombic). Pyrite is the more common so that pyrite and marcasite are often referred to collectively as pyrite or iron pyrites (Greer, 1978a).

Pyrite occurs in coal as:

1. Narrow seams or veins up to 150 mm thick and up to several hundred millimetres long.

2. Nodules. These consist of framboids (after framboise, the French for raspberry) which range from a few to several hundred micrometres in diameter, with most of them approximately 10 to 20 µm in diameter. The framboids are assemblies of octahedral crystals.

3. Discrete crystals. These individual pyrite euhedra may be widely dispersed throughout the coal. They occur predominantly in a size range of about 1–40 µm in diameter, with the large majority of the crystals being between 1–2 µm in diameter. This form of pyrite is not removed completely by physical coal cleaning methods as it is uneconomic to grind coal to this order of size.

Figure 2.2 Multi-use fuel processing test plant, San Capistrano, CA, USA (photograph courtesy of TRW Systems and Energy Corp.)

The framboid and crystalline forms of pyrite are well illustrated in Figure 2.1 which shows micrographs obtained by Greer during his studies of the microstructure of coal (Greer et al., 1980; Greer, 1979, 1978a, b, 1977a, b, 1976).

Figure 2.1 Framboidal and crystalline forms of pyrite. a, Pyrite crystals are seen attached to the upper surface of a cavity in coal. b, Pyrite crystals occurring as a cavity filling. Both individual crystals and spherical assemblies of crystals (framboids) are shown. There is infilling of material between the crystals and the framboid. c, Polycrystalline pyrite masses, infrequently observed. d, Crack filled with individual framboids of various sizes from approximately 4 to 30 µm in diameter. There is no infilling of material between framboids. e, A freshly fractured surface showing pyrite crystals within coalified plant cell network. The arrow indicates a broken cell wall revealing a single pyrite crystal within this particular cellular feature. f,g,h, Increasing magnification series for an etched surface of centimetre-sized pyrite nodule or concretion. The nodule is composed of an assembly of variously sized framboids which in this case have been joined by an infilling of additional pyrite. Within each spherical assembly of crystals (framboids) the pyrite crystal size is remarkably uniform, and yet comparison of different framboids within this field of view indicates that the pyrite crystal size varies from framboid to framboid. (Photographs courtesy of Ames Laboratory, Ames, IA, USA)

Organic sulphur

There exists very little data on the organic sulphur functions in coal (Davidson, 1980). However, it is generally assumed that the organic sulphur can be described by the following classification (Markuszewski et al., 1980):

1. Aliphatic or aromatic thiols (mercaptans, thiophenols): R–SH, Ar–SH

2. Aliphatic, aromatic or mixed sulphides (thioethers): R–S–R, Ar–S–Ar, R–S–Ar

3. Aliphatic, aromatic or mixed disulphides (bisthioethers): R–S–S–R, Ar–S–S–Ar, R–S–S–Ar

4. Heterocyclic compounds of the thiophene type (dibenzothiophene):

There is evidence to suggest that the content of thiols is substantially larger in lignites and high volatile bituminous coals than in low volatile coals. The proportion of thiophenic sulphur is also greater in higher ranked coals than in lower ones (Table 2.1, Attar and Dupuis, 1979).

Table 2.1

Distribution of organic sulphur groups in five coals

*Corrected for ‘uncounted for’ sulphur

(after Attar and Dupuis, 1979)

In general, the ratio of pyritic to organic sulphur increases as the total sulphur content of the coal increases (Table 2.2, Meyers, 1977). Hence, physical coal cleaning is useful in reducing the sulphur content of high sulphur coals but is less effective when applied to low sulphur coals.

Table 2.2

Sulphur forms in selected bituminous coals

aMoisture-free basis, pyrite plus sulphate reported as pyrite

(after Meyers, 1977)

It should be noted that significant inaccuracies can occur in the determination of pyritic and organic sulphur contents by standard analytical techniques. The total sulphur content of a coal is usually determined by a wet chemical method. The pyritic sulphur is then leached from the coal by acid and the organic sulphur determined by difference. Greer (1979) compares the organic sulphur contents of various coals determined by a standard chemical method (ASTM) with those obtained by electron microprobe X-ray analysis (EPM). Values obtained by the EPM method are up to 30% lower than those indicated by the ASTM determination. It is believed that encapsulation of the discrete pyrite crystals occurs during the acid leaching step. This residual inorganic sulphur is credited to organic sulphur. In addition, a portion of the sulphur determined as organic by the ASTM method can be elemental sulphur. Although the elemental sulphur content of coals is usually small (<0.2%), Greer (1979) quotes an exceptional example of a high sulphur coal (>6% total sulphur) in which more than 50% of the alleged organic sulphur is actually elemental sulphur. It is also difficult to obtain a representative coal sample, and this may add to the errors.

Conventional methods of analysis may not be applicable to chemically cleaned coals. Sulphur may be transformed into a form which is not present in raw coal, and therefore it may behave in an unpredictable manner when the treated coal is subjected to analysis (Wheelock, 1981).

Chapter 3

Requirements for chemically cleaned coal

Publisher Summary

This chapter presents the requirements for chemically cleaned coal. The production of coals that comply with environmental regulations for SO2 emissions when burned in large utility boilers remains the main incentive for the development of chemical coal cleaning processes. The 1971 New Source Performance Standards (NSPSs) required that emissions of SO2 to the atmosphere be limited to 0. 52 kg/GJ for large scale utility coal fired boilers. An emission of 0.52 kg/GJ is approximately equivalent to burning a coal containing between 0.6 and 0.7% sulfur without emission control equipment. These standards were met partially by the installation of flue gas desulfurization systems and partly by the use of Western United States coals of low sulfur content. To prevent the rapid depletion of these reserves of low sulfur content coals and their transportation over a long distance, the NSPSs were revised in 1979. A requirement for a 90% reduction in potential SO2 emissions was introduced except when emissions to the atmosphere are less than 0.26 kg/GJ when a 70% reduction in potential emissions is required.

The production of coals which comply with environmental regulations for SO2 emissions when burned in large utility boilers remains the main incentive for the development of chemical coal cleaning processes. In the early 1970s, when most of the development work was initiated, the US environmental regulations were less stringent than they are today. The 1971 New Source Performance Standards (NSPS) required that emissions of SO2 to the atmosphere be limited to 0.52 kg/GJ (1.2 lb/10⁶ Btu) for large scale utility coal fired boilers. An emission of 0.52 kg/GJ is approximately equivalent to burning a coal containing between 0.6 and 0.7% sulphur without emission control equipment (Meyers, 1977). These standards were met partially by the installation of flue gas desulphurisation systems (scrubbers) and partly by the use of Western US coals of low sulphur content. To prevent the rapid depletion of these reserves of low sulphur content coals and their transportation over a long distance the NSPS were revised in 1979. A requirement for a 90% reduction in potential SO2 emissions was introduced except when emissions to the atmosphere are less than 0.26 kg/GJ (0.6 lb/10⁶ Btu) when a 70% reduction in potential emissions is required.

Standards for SO2 emissions in other countries have become progressively more stringent during the last decade. It is against these standards that processes under development for the chemical cleaning of coal must be assessed (Giberti et al., 1979; Gathen, 1979).

Chapter 4

Chemistry of coal cleaning

Publisher Summary

This chapter describes the chemistry of coal cleaning. Oxidation reactions form the basis of the majority of the chemical coal cleaning processes. The exposure of coal to air results in the natural oxidation of pyrite to sulfate. It is found that when the sulfate is subsequently leached by water, the process is known as acid mine drainage. Air or oxygen is used to remove up to 30% of the organic sulfur in the Pittsburgh Energy Technology Center, Ames, Ledgemont, and ARCO processes. Greater organic sulfur removal is claimed for the JPL chlorinolysis process that uses chlorine as oxidant. The use of caustic to remove organic sulfur from coal was proposed in the mid-1960s. Masciantonio, 1965, investigated the treatment of bituminous coal with molten caustic at temperatures of between 150 and 400°C. Organic sulfur was removed from a Pittsburgh seam coal at temperatures above 200°C. Increasing the residence time and temperature increased the percentage of organic sulfur removal. The severe conditions used resulted in low yields of clean coal particularly for the Eastern Interior Basin, and Western United States coals. It is found that only 52% of a Wyoming coal was recovered from the molten caustic.

Meyers presents a fairly comprehensive review of the literature on chemical reactions of organic and pyritic sulphur suitable for use in the extraction of sulphur from coal (Meyers, 1977). However, one important omission in this review is the work of Yurovskii (1960). Yurovskii describes work concerning the origin and form of sulphur in coal, the sulphur contents of world coals and possible chemical treatments for the removal of sulphur from coal.

Reactions of pyritic sulphur

Meyers (1977) categorises the reactions of pyrite which are theoretically capable of proceeding at temperatures below the decomposition temperature of coal (approximately 400°C) as:

1. displacement reactions;

2. acid-base neutralization;

3. oxidation;

4. reduction.

The mechanism and even the products of reacting iron pyrite with a base such as NaOH are not well defined. However, sodium sulphide and sodium thiosulphate have been identified in the products of the reaction, suggesting the overall reaction (Attar 1980):

(4.1)

The exposure of coal to air results in the natural oxidation of pyrite to sulphate. When the sulphate is subsequently leached by water the process is known as ‘acid mine drainage’ (Agarwal et al., 1975). Virtually all the mechanisms reported in the literature for the removal of pyrite from coal are attempts to enhance this natural oxidation process. Oxidants ranging from metal ions (Fe³+, Hg²+, Ag+) and strong acids (HNO3 and HClO4) to O2, Cl2, SO2 and H2O2 have sufficient oxidation potential to react with pyrite (Meyers, 1977). The use of ferric sulphate as an oxidant has been investigated by Mixon and Vermeulen (1979) and applied in the TRW Meyers process (Meyers, 1977).

Several reactions involving the reduction of pyrite are reported in the literature. However, the consumption of expensive reducing agents precludes the commercial application of this type of reaction (Mesher and Peterson, 1979).

Mesher and Peterson (1979) investigated a fifth type of reaction using sodium sulphide and sodium polysulphide to extract zero valent sulphur from pyrite to form ferrous sulphide (FeS):

(4.2)

(4.3)

The coal was subsequently washed with a weak HCl solution to decompose the ferrous sulphide to H2S and FeCl2:

(4.4)

However, only 50% of the pyritic sulphur was removed after several hours of treatment at 250°C.

Reactions of organic sulphur

Because organic sulphur is present in petroleum in structural forms analogous to those in coal, Meyers (1977) suggested the following reactions for the removal of organic sulphur from coal, based on the experience of the oil refining industry:

1. solvent partition;